CN103788298A - Preparation method of carboxylated nitrile latex and article prepared from carboxylated nitrile latex - Google Patents
Preparation method of carboxylated nitrile latex and article prepared from carboxylated nitrile latex Download PDFInfo
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- 239000004816 latex Substances 0.000 title claims abstract description 77
- 229920000126 latex Polymers 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 150000002825 nitriles Chemical class 0.000 title abstract 5
- 238000000034 method Methods 0.000 claims abstract description 101
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 32
- XNINAOUGJUYOQX-UHFFFAOYSA-N 2-cyanobutanoic acid Chemical compound CCC(C#N)C(O)=O XNINAOUGJUYOQX-UHFFFAOYSA-N 0.000 claims description 63
- 239000000203 mixture Substances 0.000 claims description 58
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 239000003995 emulsifying agent Substances 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 20
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 18
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 18
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 18
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 18
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 18
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 18
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 17
- 230000002829 reductive effect Effects 0.000 claims description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- 150000001735 carboxylic acids Chemical class 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 230000009466 transformation Effects 0.000 claims description 12
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 11
- 230000000740 bleeding effect Effects 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- 239000013530 defoamer Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 238000004332 deodorization Methods 0.000 claims description 7
- 239000006174 pH buffer Substances 0.000 claims description 7
- 239000012744 reinforcing agent Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- RMGVZKRVHHSUIM-UHFFFAOYSA-L dithionate(2-) Chemical compound [O-]S(=O)(=O)S([O-])(=O)=O RMGVZKRVHHSUIM-UHFFFAOYSA-L 0.000 claims description 6
- 150000002978 peroxides Chemical class 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- -1 triazines nitrogen-containing heterocycle compound Chemical class 0.000 claims description 6
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 229920013701 VORANOL™ Polymers 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004160 Ammonium persulphate Substances 0.000 claims description 3
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- JTUOMQJVPHRJHA-UHFFFAOYSA-N [C].C(CCCCCCCCCCC)S Chemical compound [C].C(CCCCCCCCCCC)S JTUOMQJVPHRJHA-UHFFFAOYSA-N 0.000 claims description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 3
- MTCQXZCDHOPYSZ-UHFFFAOYSA-N azanium;n,n-dimethylcarbamodithioate Chemical compound [NH4+].CN(C)C([S-])=S MTCQXZCDHOPYSZ-UHFFFAOYSA-N 0.000 claims description 3
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 claims description 3
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 3
- 229950004394 ditiocarb Drugs 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 230000008676 import Effects 0.000 claims description 3
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001558 organosilicon polymer Polymers 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- VISBXDUCQXTFDL-UHFFFAOYSA-L potassium sodium N,N-dimethylcarbamodithioate Chemical compound CN(C([S-])=S)C.[K+].CN(C([S-])=S)C.[Na+] VISBXDUCQXTFDL-UHFFFAOYSA-L 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 11
- 239000000376 reactant Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 210000005056 cell body Anatomy 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000013589 supplement Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000010198 maturation time Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Polymerisation Methods In General (AREA)
Abstract
The invention provides a preparation method of carboxylated nitrile butadiene latex and an article prepared from the carboxylated nitrile butadiene latex. The method adopts one-time feeding to mix the required reactants and adopts a gradient heating mode to carry out emulsion polymerization reaction. The method has excellent conversion rate and stability, and the product prepared by the carboxylated nitrile butadiene latex has good tensile strength and elongation.
Description
Technical field
The present invention is about a kind of preparation method of latex, especially about a kind of preparation method and prepared article of this carboxyl butyronitrile latex of carboxyl butyronitrile latex.
Background technology
Butyronitrile latex (NBR) is the latex that utilizes the monomer copolymerization such as divinyl and vinyl cyanide to form.By the prepared emgloves of butyronitrile latex, because thering is good oil resistant and endurance, be to be very widely used in the commodity that industry is used with the people's livelihood.In order to improve film-forming properties, chemical resistance and mechanical properties and the Application Areas thereof of butyronitrile latex itself, recently develop by adding the strategy containing carboxyl and ester group grade in an imperial examination three and the 4th monomer, to carry out the modification of butadiene-acrylonitrile polymer.Carboxyl butyronitrile latex (XNBR) also replaces butyronitrile latex gradually because of better wearing quality, becomes market mainstream product.
The preparation of carboxyl butyronitrile latex mainly comprises emulsion polymerization reaction, and its reaction raw materials can be divided into reaction monomers, emulsifying agent and three large classes of initiator.Reaction monomers is still take divinyl and vinyl cyanide as main flow, then other functional monomer that arranges in pairs or groups.Described functional monomer is the performance (as chemical resistance, extension pulling force and tensile strength) for strengthening latex.Described functional monomer comprises unsaturated carboxylic acid (vinylformic acid, methacrylic acid or toxilic acid) and/or esters of unsaturated carboxylic acids (butyl acrylate or methyl methacrylate and derivative thereof).
According to selected initiator system, in this area, the preparation of carboxyl butyronitrile latex can be divided into high temperature polymerization (persulphate) and two kinds of low temperature polymerizations (oxidation-reduction system).High-temperature polymerization has speed of reaction faster, but also therefore causes the shortcoming that is difficult to control reaction stability.Therefore, reaction stability and synthetic after under the dual consideration of latex characteristic, low temperature polymerization method is selected method in this area comparatively.But low temperature polymerization method speed of reaction shortcoming slow and low conversion rate is still suddenly treated further to overcome.
In addition, in the preparation of traditional carboxyl butyronitrile latex, need to add if the inorganic assistant agents such as sulphur, zinc oxide, promotor, anti-aging agent are to strengthen its mechanical property.These inorganic assistant agents are unavoidable the latex solution generation deposited phenomenon that makes, and produce on the running of machine and the QC of gloves finished product and cause difficulty for gloves.More very it, adding sulphur needs maturation time of about 24-48 hour as linking agent, not only extends the production time, this sulfur cross-linking agent also easily causes irritated or other doubt on healthy of user.
In sum, still there is the shortcoming that many needs overcome in the preparation method of traditional carboxyl butyronitrile latex.Because the utilization of latex material is increasingly extensive, in this area in the urgent need to a kind of more appropriate method of preparing carboxyl butyronitrile latex.
Summary of the invention
One of object of the present invention is for a kind of preparation method of carboxyl butyronitrile latex is provided, and it mainly adopts low temperature polymerization reaction, but has outstanding turnover ratio.The method does not need to add sulfur cross-linking agent, therefore can reduce the doubt of health risk and environment, and has advantages of the process time of shortening.
Another object of the present invention is for providing the latex product of preparation method's gained of this carboxyl butyronitrile latex.
For achieving the above object, the invention provides a kind of preparation method of carboxyl butyronitrile latex, it comprises following steps: a. obtains a mixture, and it comprises divinyl, vinyl cyanide, functional monomer, emulsifying agent, initiator and solvent; B. make described mixture react in following condition: 3.5 to 8.0Kgf/cm
2pressure and the temperature of 10 to 25 ℃; C. make to react in following condition through the reacted mixture of above-mentioned steps b: 4.5 to 8.0Kgf/cm
2pressure and the temperature of 35 to 45 ℃; D. make to react in following condition through the reacted mixture of above-mentioned steps c: 4.5 to 8.0Kgf/cm
2pressure and the temperature of 45 to 55 ℃; And e. adds terminator, and make to react in following condition through the reacted mixture of above-mentioned steps d :-0.9 to 0.1Kgf/cm
2pressure and the temperature of 35 to 45 ℃, make described carboxyl butyronitrile latex; Wherein, described functional monomer comprises unsaturated carboxylic acid.
In aforesaid method, preferably, the mixture in step a comprises: the divinyl of 20.0 to 25.0 weight parts; The vinyl cyanide of 10.0 to 15.0 weight parts; The unsaturated carboxylic acid of 2.0 to 5.0 weight parts; The initiator of 0.5 to 2.0 weight part; The emulsifying agent of 1.0 to 2.5 weight parts; And the solvent of 35.0 to 45.0 weight parts.
In aforesaid method, preferably, described functional monomer further comprises esters of unsaturated carboxylic acids, in the mixture of described esters of unsaturated carboxylic acids in described step a, accounts for: 0.1 to 3.0 weight part.
In aforesaid method, preferably, the mixture in described step a further comprises: the pH buffer reagent of 0.1 to 0.5 weight part.
In aforesaid method, preferably, the mixture in described step a further comprises: the chain-transfer agent of 0.1 to 0.5 weight part.
In aforesaid method, preferably, the mixture in described step a further comprises: the structural reinforcing agent of 0.1 to 1.0 weight part.
In aforesaid method, preferably, described unsaturated carboxylic acid is: the combination of one or more in methacrylic acid, vinylformic acid and toxilic acid.
In aforesaid method, preferably, described initiator is oxidized form initiator.More preferably, described oxidized form initiator is inorganic peroxide.Most preferably, described inorganic peroxide is: the combination of one or more in Sodium Persulfate, Potassium Persulphate and ammonium persulphate.
In aforesaid method, preferably, described emulsifying agent is: the combination of one or more in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, oxyethane lauryl alcohol and Voranol EP 2001.
In aforesaid method, preferably, described solvent is: water, Virahol or its combination.
In aforesaid method, preferably, described esters of unsaturated carboxylic acids is: butyl acrylate, butyl methacrylate, isobutyl acrylate, the misery butyl ester of propylene, Octyl methacrylate or its combination.
In aforesaid method, preferably, described pH buffer reagent is: the combination of one or more in carbonate, phosphoric acid salt and pyrophosphate salt.
In aforesaid method, preferably, described chain-transfer agent is: tert-dodecyl mercaptan, dodecyl mercaptan carbon or its combination.
In aforesaid method, preferably, described structural reinforcing agent is: triazines nitrogen-containing heterocycle compound, trifunctional base aziridine cpd or its combination.
In aforesaid method, preferably, it does not comprise sulfur cross-linking agent.
In aforesaid method, preferably, the preparation of described mixture is to be first a premixture by described vinyl cyanide, described functional monomer, described emulsifying agent and described solvent, then add described divinyl and described initiator in described premixture to form described mixture.
In aforesaid method, preferably, step b carries out 7.0 to 15.0 hours.
In aforesaid method, preferably, step c carries out 2.0 to 6.0 hours.
In aforesaid method, preferably, steps d is carried out 4.5 to 8.5 hours.
In aforesaid method, preferably, after step b completes, within 30 minutes by temperature increase to 35 to 45 ℃, to carry out step c.
In aforesaid method, preferably, after step c completes, within 30 minutes by temperature increase to 45 to 55 ℃, to carry out steps d.
In aforesaid method, preferably, after step b completes, add after an emulsifying agent and a reductive agent, then carry out step c.
In aforesaid method, preferably, after step c completes, add after an emulsifying agent and a reductive agent, then carry out steps d.
In aforesaid method, preferably, described emulsifying agent is one or more the combination combination in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, oxyethane lauryl alcohol and Voranol EP 2001.
In aforesaid method, preferably, described reductive agent is one or more the combination in Sodium Metabisulphate 65, sodium bisulfite and ferrous sulfate.
In aforesaid method, preferably, the addition of the described terminator of step e is 50 to 400ppm.
In aforesaid method, preferably, described terminator is one or more the combination in Sodium dimethyldithiocarbamate 40min, Thiocarb, potassium dimethyldithiocarbamate sodium, dimethyl dithiocarbamic acid ammonium, Resorcinol and diethyl hydroxylamine.
In aforesaid method, preferably, it is 7.5 to 8.5 that step e further comprises adjustment pH value.
In aforesaid method, preferably, step e further comprises interpolation one deodorization agent.More preferably, described deodorization agent is Acrylic emulsion deodovization agent.
In aforesaid method, preferably, step e further comprises interpolation one defoamer.More preferably, described defoamer is organosilicon polymer, Dormant oils or its combination.
In aforesaid method, preferably, after step e, further comprise a step f, step f is in-3.0 to-5.0Kgf/cm
2pressure under carry out following steps: import nitrogen; Bleed, and stir through the reacted mixture of step e; Stop importing nitrogen; Stop bleeding; And carry out filtration step.
In aforesaid method, preferably, it is to carry out at the temperature of in 10 to 55 ℃.
In aforesaid method, preferably, its transformation efficiency is minimum is 90%.More preferably, its transformation efficiency is minimum is 96%.
The present invention provides again a kind of carboxyl butyronitrile latex product, and it is to make take the prepared carboxyl butyronitrile latex of preceding method as raw material, and its tensile strength is 20 to 25Mpa, and its unit elongation is 550 to 700%.
According to the specific embodiment of the present invention, preferably, described carboxyl butyronitrile latex product is gloves or dress ornament etc.
In sum, the preparation method of carboxyl butyronitrile latex of the present invention adopts the mode of disposable pan feeding and gradient increased temperature to carry out, and makes method of the present invention possess the advantage of the high stability of low temperature polymerization and the high conversion of high temperature polymerization.Therefore, not only can prepare the latex product of tensile strength and unit elongation excellence, this method more can overcome traditional method for making low-conversion and expend the shortcoming of maturation time.
Accompanying drawing explanation
Fig. 1 is the preparation method's of carboxyl butyronitrile latex of the present invention schema.
Fig. 2 is the schema of step f in the preparation method of carboxyl butyronitrile latex of the present invention.
Primary clustering nomenclature:
101 step a
102 step b
103 step c
104 steps d
105 step e
106 step f
201 stirrings of bleeding
202 stirrings of bleeding
Embodiment
In the preparation method of carboxyl butyronitrile latex, reaction conditions (temperature and pressure), feeding manner and degassed step are the important factors of the quality of the prepared carboxyl butyronitrile latex of impact.Accordingly, carboxyl butyronitrile latex preparation method's of the present invention main concept is " disposable pan feeding " and " gradient increased temperature ", to possess the advantage of the high stability of traditional low temperature polymerization and the high conversion of high temperature polymerization simultaneously.And the inventive method does not need additionally to add sulfur cross-linking agent, be of value to environment and user's health.In addition the work-ing life that, the degassed step in preparation method of the present invention contributes to maintain the stability of carboxyl butyronitrile latex and extends cell body in technique.
What is called of the present invention " disposable pan feeding " refers to before emulsion polymerization reaction (before carrying out gradient increased temperature), just completes the mixing of all required divinyl, vinyl cyanide, functional monomer, emulsifying agent, solvent and initiator.In a preferred embodiment of the invention, can in follow-up emulsion polymerization reaction, additionally add emulsifying agent and the reductive agent of at least 1 time, so that emulsion polymerization reaction is more complete, and promote the transformation efficiency of the inventive method.
What is called of the present invention " gradient increased temperature " refers in integrated artistic, makes to discontinuity reaction raw materials react in different temperature stratum.This mode is for prior to carrying out emulsion polymerization reaction under low temperature environment to improve stability, then, is to carry out emulsion polymerization reaction to improve transformation efficiency under hot environment.The definition of described low temperature environment and described hot environment is respectively according to the reaction environment of low temperature polymerization well known in the art and high temperature polymerization.More clearly, described low temperature environment refers to 10 to 25 ℃; And described hot environment refers to 45 to 55 ℃.
Refer to Fig. 1, the preparation method of carboxyl butyronitrile latex of the present invention at least comprises: in step a 101, mix required reactant, then sequentially carry out the first stage polyreaction 7.0 to 15.0 hours, the subordinate phase polyreaction 2.0 to 6.0 hours of step c 103 of step b 102 and the phase III polyreaction of steps d 104 4.5 to 8.5 hours, then add terminator and carry out step e 105 with stopped reaction, finally enter step f106 and carry out follow-up remaining monomer processing and filtration treatment.Between described step b 102 and described step c 103 and/or between described step c 103 and described steps d 104, can optionally add a supplementary liquid so that react more complete.Described supplementary liquid can comprise emulsifying agent, reductive agent or its combination.
Details are as follows for the each step of the inventive method:
A) prepare a reacting material mixture
Reaction raw materials is imported to a reactive tank.The divinyl that described reaction raw materials comprises 20.0 to 25.0 weight parts; The vinyl cyanide of 10.0 to 15.0 weight parts; The unsaturated carboxylic acid of 2.0 to 5.0 weight parts; The initiator of 0.5 to 2.0 weight part; The emulsifying agent of 1.0 to 2.5 weight parts; And the solvent of 35.0 to 45.0 weight parts.
In an embodiment, described reaction raw materials further comprises the esters of unsaturated carboxylic acids of 0.1 to 3.0 weight part, pH buffer reagent, the chain-transfer agent of 0.1 to 0.5 weight part and/or the structural reinforcing agent of 0.1 to 1.0 weight part of 0.1 to 0.5 weight part.Described unsaturated carboxylic acid and/or described esters of unsaturated carboxylic acids are functional monomer used in the inventive method.
In a preferred embodiment, the preparation of described mixture is to be first a premixture by described vinyl cyanide, described functional monomer (comprising described unsaturated carboxylic acid and/or described esters of unsaturated carboxylic acids), described emulsifying agent and described solvent, then add described divinyl and described initiator in described premixture to form described mixture.In this preferred implementation, all required reactants are still before emulsion polymerization reaction (before carrying out gradient increased temperature) and complete mixing, therefore the feature of " disposable pan feeding " according to the invention still.
Described divinyl and described vinyl cyanide are the principal reaction things in the inventive method, and described functional monomer (comprising described unsaturated carboxylic acid and/or described esters of unsaturated carboxylic acids) is that the carboxyl butyronitrile latex wanting to make in order to modification is to promote its chemical resistance, to uphold pulling force and tensile strength.Described unsaturated carboxylic acid includes, but are not limited to: the combination of one or more in methacrylic acid, vinylformic acid and toxilic acid.Described esters of unsaturated carboxylic acids includes, but are not limited to: the combination of one or more in butyl acrylate, butyl methacrylate, the misery butyl ester of propylene and Octyl methacrylate.
Described emulsifying agent can be: anionic emulsifier and/or nonionic emulsifier.Described emulsifying agent comprises, but is not limited to: the combination of one or more in alkyl sodium sulfonate, sodium alkyl sulfate, fatty alcohol-polyoxyethylene ether and potassium oleate.Described emulsifying agent is except having the effect of impelling reacting balance, also because it is for peptizer sensitivity, and makes the easy deemulsification of latex solution and fast filming contributes to the preparation of follow-up latex product.
Preferably, described solvent is: water, Virahol or its combination.More preferably, described water is deionized water.Preferably, described initiator is oxidized form initiator, for example: inorganic peroxide.Described inorganic peroxide includes, but are not limited to: the combination of one or more in Sodium Persulfate, Potassium Persulphate and ammonium persulphate.
Described pH buffer reagent is the carrying out in order to stablize W-response, and it includes, but are not limited to: the combination of one or more in carbonate, phosphoric acid salt and pyrophosphate salt.Described chain-transfer agent is the molecular weight of controlling prepared carboxyl butyronitrile latex, so that it falls within desired molecular weight ranges.Described chain-transfer agent includes, but are not limited to: tert-dodecyl mercaptan, dodecyl mercaptan carbon or its combination.
Described structural reinforcing agent includes, but are not limited to: triazines nitrogen-containing heterocycle compound, trifunctional base aziridine cpd or its combination.For instance, described structural reinforcing agent is: trimeric cyanamide, San poly cyanamid Jia Chuo resin or its combination.
Feasible ground, described triazines nitrogen-containing heterocycle compound has following structural 1:
Wherein, R
1with R
2be respectively H, CH
2oH or CH
2oCH
3.
Feasible ground, described trifunctional base aziridine cpd compound has following structural 2:
Wherein, R
3for CH
3or OH; R
4for CH
3or H.
B) first stage emulsion polymerization reaction
In step b, make to react in following condition through the reacted mixture of step a by pressure valve and temperature-control device: 3.5 to 8.0Kgf/cm
2pressure and the temperature of 10 to 25 ℃.In a preferred implementation, make in the first stage, to react 7.0 to 15.0 hours through the reacted mixture of step a, and in 30 minutes, make thereafter temperature and pressure be adjusted to the required temperature of subsequent step c and pressure.
In a preferred implementation, make through the reacted mixture of step a after reacting 7.0 to 15.0 hours in the first stage, further add one first and supplement liquid to mixture, so that subsequent reactions promotes transformation efficiency more completely.Described first supplements liquid comprises above-mentioned emulsifying agent and a reductive agent.Described reductive agent includes, but are not limited to: the combination of one or more in Sodium Metabisulphate 65, S-WAT and sodium bisulfite.
C) subordinate phase emulsion polymerization reaction
In step c, make to react in following condition through the reacted mixture of step b by pressure valve and temperature-control device: 4.5 to 8.0Kgf/cm
2pressure and the temperature of 35 to 45 ℃.In a preferred implementation, make in subordinate phase, to react 2.0 to 6.0 hours through the reacted mixture of step b, and in 30 minutes, make thereafter temperature and pressure be adjusted to the required temperature of subsequent step d and pressure.
In a preferred implementation, make through the reacted mixture of step b after reacting 2.0 to 6.0 hours in subordinate phase, further add one second and supplement liquid to mixture, so that subsequent reactions promotes transformation efficiency more completely.Described second supplements liquid comprises above-mentioned emulsifying agent and a reductive agent.Described reductive agent includes, but are not limited to: the combination of one or more in Sodium Metabisulphate 65, S-WAT and sodium bisulfite.
D) phase III emulsion polymerization reaction
In steps d, make to react in following condition through the reacted mixture of step c by pressure valve and temperature-control device: 4.5 to 8.0Kgf/cm
2pressure and the temperature of 45 to 55 ℃.In a preferred implementation, make through the reacted mixture of step c after reacting 4.5 to 8.5 hours in the phase III, reduce mixing speed and start pressure release.
E) termination reaction
By pressure valve and temperature-control device, pressure is adjusted in-0.9 to 0.1Kgf/cm
2, and make temperature adjust in 35 to 45 ℃.Then add terminator, make reaction be maintained at 0.25-0.5 hour under above-mentioned pressure and temperature condition.Then,, after adding dislocation agent and/or defoamer, by carry out follow-up degassed step in groove is bled in the reacted mixture immigration one of step e, (step f).
In an embodiment, the addition of described terminator is 50 to 400ppm.Described terminator includes, but are not limited to: the combination of one or more in Sodium dimethyldithiocarbamate 40min, Thiocarb, potassium dimethyldithiocarbamate sodium, dimethyl dithiocarbamic acid ammonium, Resorcinol and diethyl hydroxylamine.In a preferred implementation, the pH value of adjusting the mixture in above-mentioned steps e is 7.5 to 8.5.In an embodiment, carry out the adjustment of pH with an alkali lye.Described alkali lye includes, but are not limited to: ammoniacal liquor, potassium hydroxide aqueous solution or its combination.In an embodiment, described deodorization agent is Acrylic emulsion deodovization agent.Preferably, the addition of described deodorization agent is 100 to 1000ppm.In an embodiment, described defoamer is organosilicon polymer, Dormant oils or its combination.Preferably, the addition of described defoamer is 100 to 1000ppm.
F) degassed step
The pressure of bleeding in groove by pressure valve adjustment is-3.0 to-5.0Kgf/cm
2, and import nitrogen make its reaction 3 to 5 hours; Wherein, bleed down in continuing, continue in steel basin through the reacted mixture of step e so that react completely.Then stop bleeding, then by temperature-control device, temperature is down to after room temperature, move in filtration unit and carry out filtration step, can obtain prepared carboxyl butyronitrile latex.Described filtration step can adopt means well known in the art to carry out, and it includes, but are not limited to: the combination of one or more in bag filter, plate-type filtering, vane type filtration, cross flow filtration and membrane filtration.
More clearly, refer to Fig. 2, step f of the present invention starts to bleed pass into nitrogen under liquid after to stir 201.The stirring 201 of bleeding carried out 2 after 3 hours, stopped passing into nitrogen, then proceeded to bleed and stir 202.Stir and 2021 after 2 hours, stop bleeding in bleeding, and by reaction product in groove by a filtration unit to carry out filtration step, then obtain prepared carboxyl butyronitrile latex.
Affiliated field those skilled in the art should understand, and described step e has made carboxyl butyronitrile latex, and described step f is for removing reaction residual monomer to improve the purity of prepared carboxyl butyronitrile latex.Affiliated field those skilled in the art can optionally select whether to carry out described step f.Carry out described step f if do not want, when can, after described step e, obtaining prepared carboxyl butyronitrile latex through suitable filter.
The prepared carboxyl butyronitrile latex of the present invention can be used as the raw material of latex product.Described goods include, but are not limited to: gloves or dress ornament.With the example that is prepared as of carboxyl butyronitrile emgloves, can adopt method for making well known in the art to carry out, briefly: the potassium hydroxide of the deionized water of the titanium dioxide of the zinc oxide of the carboxyl butyronitrile latex of 100.0 weight parts, 0.6 to 1.0 weight part, 1.5 to 2.0 weight parts, 35.0 to 45.0 weight parts and 0.2 to 0.3 weight part mix and blend 2 in a cell body, to 4 hours, is obtained to a mixture.Then, the mixture of gained is evenly built-up in and is soaked in advance on the fingerprint of putting peptizer, and synchronously carry out surface treatment.Then, the fingerprint that attaches described mixture is placed at 115 to 125 ℃ and toasts 15 to 25 minutes.Finally, carry out, after other required subsequent disposal, making a carboxyl butyronitrile emgloves.
Following examples are for further understanding advantage of the present invention, not for limiting the scope of the invention.Embodiment 1: prepare carboxyl butyronitrile latex with the inventive method
Pan feeding
By the deionized water of 43.0 weight parts, the mixture (emulsifying agent of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and the oxyethane lauryl alcohol of totally 1.0 weight parts; The weight ratio of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and oxyethane lauryl alcohol is 1: 1: 1), the tert-dodecyl mercaptan (chain-transfer agent) of the butyl acrylate of the carbonate (pH buffer reagent) of 0.1 weight part, 2.0 weight part methacrylic acids, 2.0 weight parts, 0.2 weight part, add in cell body with the vinyl cyanide of 12.0 weight parts.Confirm that cell body carries out mix and blend after airtight.Then by groove with groove in air in mixture be replaced into completely after nitrogen, stop vacuumizing, and the divinyl of 22.0 weight parts injected in cell body to the initiator of 0.2 weight part that finally reinjects.
Reaction is controlled with supplementary liquid and is added
At 25 ℃, utilize nitrogen that groove internal pressure is adjusted into 4.0Kgf/cm
2and start to carry out first stage polyreaction.This first stage polyreaction was carried out after 9.0 hours, added and supplemented for the first time liquid (Sodium Metabisulphate 65 of the mixture of the sodium lauryl sulphate of totally 0.05 weight part, Sodium dodecylbenzene sulfonate and oxyethane lauryl alcohol (weight ratio of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and oxyethane lauryl alcohol is 1: 1: 1) and 0.1 weight part).Then (groove internal pressure is adjusted into 3.9Kgf/cm, by the mode of gradient increased temperature, temperature to be promoted to 40 ℃ in 30 minutes
2) to carry out subordinate phase polyreaction.
This subordinate phase polyreaction was carried out after 4.5 hours, add and supplement for the second time liquid (Sodium Metabisulphate 65 of the sodium lauryl sulphate of totally 0.05 weight part, Sodium dodecylbenzene sulfonate and oxyethane lauryl alcohol mixture (weight ratio of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and oxyethane lauryl alcohol is 1: 1: 1) and 0.1 weight part), same by the mode of gradient increased temperature again, temperature was promoted to 50 ℃ in 30 minutes, and (groove internal pressure is adjusted into 5.0Kgf/cm
2) to carry out phase III reaction.
This phase III polyreaction was carried out after 8.0 hours, recorded in cell body after the transformation efficiency of reactant reaches more than 96%, reduced mixing speed and also started pressure release, treated that groove internal pressure is 0Kgf/cm
2time, the temperature in reactive tank is down to 45 ℃ and add terminator.Then, the pH value of adjusting the reactant in reactive tank with alkali lye is to 7.5-8.5, and reacts after 30 minutes in holding warm steel basin, adds deodorization agent and defoamer, afterwards the reactant in reactive tank moved into the degassed step of carrying out follow-up vacuum suction in the groove of bleeding.
Residual monomer removes and aftertreatment (degassed step)
In the groove of bleeding, vacuum tightness is adjusted to-0.3Kgf/cm
2after, make it react 2.0 hours to remove residual monomer by the mode of logical nitrogen under liquid level.Finally, temperature is down to after room temperature, carries out filtration step, obtain the carboxyl butyronitrile latex of the present embodiment.
Embodiment 2: prepare carboxyl butyronitrile latex with the inventive method
Prepare carboxyl butyronitrile latex with the method described in embodiment 1, but, wherein the usage quantity of methacrylic acid changes 3.0 weight parts into, the usage quantity of butyl acrylate changes 1.0 weight parts into, and the usage quantity of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and oxyethane lauryl alcohol mixture changes 1.1 weight parts (weight ratio of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and oxyethane lauryl alcohol is 1: 1: 1) into.
Embodiment 3: prepare carboxyl butyronitrile latex with the inventive method
Prepare carboxyl butyronitrile latex with the method described in embodiment 1, but, wherein the usage quantity of methacrylic acid changes 3.0 weight parts into, the usage quantity of butyl acrylate changes 1.0 weight parts into, and the usage quantity of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and oxyethane lauryl alcohol mixture changes 1.1 weight parts (weight ratio of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and oxyethane lauryl alcohol is 1: 1: 1) into.In addition, the time of first stage polyreaction changes 13.0 hours into, and the time of subordinate phase polyreaction changes 3.0 hours into, and the time of phase III polyreaction changes 6.0 hours into.
Embodiment 4: prepare carboxyl butyronitrile latex with the inventive method
Prepare carboxyl butyronitrile latex with the method described in embodiment 1, but, wherein the usage quantity of methacrylic acid changes 3.0 weight parts into, the usage quantity of butyl acrylate changes 1.0 weight parts into, and the usage quantity of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and oxyethane lauryl alcohol mixture changes 1.1 weight parts (weight ratio of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and oxyethane lauryl alcohol is 1: 1: 1) into.In addition, the time of first stage polyreaction changes 13.0 hours into and temperature changes 15 ℃ into, and the time of subordinate phase polyreaction changes 3.0 hours into, and the time of phase III polyreaction changes 6.0 hours into.
Embodiment 5: prepare carboxyl butyronitrile latex with the inventive method
Prepare carboxyl butyronitrile latex with the method described in embodiment 1, but, wherein the usage quantity of methacrylic acid changes 3.0 weight parts into, the usage quantity of butyl acrylate changes 1.0 weight parts into, and the usage quantity of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and oxyethane lauryl alcohol mixture changes 1.1 weight parts (weight ratio of sodium lauryl sulphate, Sodium dodecylbenzene sulfonate and oxyethane lauryl alcohol is 1: 1: 1) into.In addition, the time of first stage polyreaction changes 13.0 hours into and temperature changes 15.0 ℃ into, and the time of subordinate phase polyreaction changes 3.0 hours into, and the time of phase III polyreaction changes 6.0 hours into.In addition, then after described degassed step, separately add the trimeric cyanamide of 0.2 weight part.
Embodiment 6: physical property detects
In the present embodiment, by detecting every character of above-described embodiment 1 to embodiment 5 prepared carboxyl butyronitrile latex, comprising: transformation efficiency, solid, viscosity, pH value, particle diameter, acrylonitrile content and acrylonitrile residue.In addition, use above-described embodiment 1 to embodiment 5 prepared carboxyl butyronitrile latex to prepare respectively a carboxyl butyronitrile emgloves for raw material, and with mutually compare with the commercially available prepared gloves of carboxyl butyronitrile latex (comparative example 1) containing sulphur linking agent.
Every character of carboxyl butyronitrile latex of the present invention as listed in Table 1.In addition, the character of carboxyl butyronitrile emgloves of the present invention and the commercially available carboxyl butyronitrile emgloves that contains sulfur cross-linking agent is as listed in table 2.
Every character of the carboxyl butyronitrile latex of table 1: embodiment 1 to embodiment 5
| Embodiment | Transformation efficiency | Solid | Viscosity | PH value | Particle diameter | Acrylonitrile content | Acrylonitrile residue |
| 1 | ＞96％ | 43.4％ | 30cps | 8.5 | 130nm | 24.5％ | ≤100ppm |
| 2 | ＞96％ | 43.2％ | 25cps | 8.5 | 127nm | 24.8％ | ≤100ppm |
| 3 | ＞94％ | 43.5％ | 30cps | 8.5 | 133nm | 24.0％ | ≤100ppm |
| 4 | ＞93％ | 43.7％ | 25cps | 8.5 | 135nm | 24.0％ | ≤100ppm |
| 5 | ＞93％ | 43.8％ | 26cps | 8.5 | 136nm | 24.0％ | ≤100ppm |
Table 2: the character comparison of carboxyl butyronitrile emgloves
| Sample | Tensile strength | Unit elongation | Outward appearance |
| Embodiment 1 | 20.5Mpa | 650％ | Brilliant white |
| Embodiment 2 | 21.5Mpa | 680％ | Brilliant white |
| Embodiment 3 | 20.8Mpa | 550％ | Brilliant white |
| Embodiment 4 | 22.0Mpa | 700％ | Brilliant white |
| Embodiment 5 | 25.0Mpa | 640％ | Brilliant white |
| Comparative example 1 | 16.4Mpa | 550％ | Brilliant white |
From institute's column data in above-mentioned table 1, the inventive method has excellent transformation efficiency, and in addition, from the data in above-mentioned table 2, carboxyl butyronitrile emgloves of the present invention has good tensile strength and unit elongation.Accordingly, the inventive method does not need to use sulfur cross-linking agent and has advantages of saves time and useful environment and user's health, and prepared carboxyl butyronitrile latex product has more commercially available carboxyl butyronitrile latex product tensile strength and unit elongation can't be obtained.Therefore, the inventive method is particularly suitable for applying to the preparation of carboxyl butyronitrile latex product, for example, and the disposable glove of technical grade, medical grade or electronic-grade or the preparation of dress ornament.
Affiliated field those skilled in the art work as and can understand, under spirit of the present invention, and the various variations that can carry out according to embodiment of the present invention.Therefore, obvious listed embodiment is not in order to limit the present invention, but attempt is under asked protection domain, is covered by the modification of making in spirit of the present invention and category.
Claims (40)
1. a preparation method for carboxyl butyronitrile latex, it comprises following steps:
A. obtain a mixture, it comprises divinyl, vinyl cyanide, functional monomer, emulsifying agent, initiator and solvent;
B. make described mixture react in following condition: 3.5 to 8.0Kgf/cm
2pressure and the temperature of 10 to 25 ℃;
C. make to react in following condition through the reacted mixture of above-mentioned steps b: 4.5 to 8.0Kgf/cm
2pressure and the temperature of 35 to 45 ℃;
D. make to react in following condition through the reacted mixture of above-mentioned steps c: 4.5 to 8.0Kgf/cm
2pressure and the temperature of 45 to 55 ℃; And
E. add terminator, and make to react in following condition through the reacted mixture of above-mentioned steps d :-0.9 to 0.10Kgf/cm
2pressure and the temperature of 35 to 45 ℃, make described carboxyl butyronitrile latex;
Wherein, described functional monomer comprises unsaturated carboxylic acid.
2. the method for claim 1, wherein the mixture in step a comprises:
The divinyl of 20.0 to 25.0 weight parts;
The vinyl cyanide of 10.0 to 15.0 weight parts;
The unsaturated carboxylic acid of 2.0 to 5.0 weight parts;
The initiator of 0.5 to 2.0 weight part;
The emulsifying agent of 1.0 to 2.5 weight parts; And
The solvent of 35.0 to 45.0 weight parts.
3. method as claimed in claim 2, wherein, described functional monomer further comprises esters of unsaturated carboxylic acids, in the mixture of described esters of unsaturated carboxylic acids in described step a, accounts for: 0.1 to 3.0 weight part.
4. method as claimed in claim 2, wherein, the mixture in described step a further comprises: the pH buffer reagent of 0.1 to 0.5 weight part.
5. method as claimed in claim 2, wherein, the mixture in described step a further comprises: the chain-transfer agent of 0.1 to 0.5 weight part.
6. method as claimed in claim 2, wherein, the mixture in described step a further comprises: the structural reinforcing agent of 0.1 to 1.0 weight part.
7. the method as described in any one in claim 1-6, wherein, described unsaturated carboxylic acid is: the combination of one or more in methacrylic acid, vinylformic acid and toxilic acid.
8. the method as described in any one in claim 1-6, wherein, described initiator is oxidized form initiator.
9. method as claimed in claim 8, wherein, described oxidized form initiator is inorganic peroxide.
10. method as claimed in claim 9, wherein, described inorganic peroxide is: the combination of one or more in Sodium Persulfate, Potassium Persulphate and ammonium persulphate.
11. methods as described in any one in claim 1-6, wherein, described emulsifying agent is: the combination of one or more in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, oxyethane lauryl alcohol and Voranol EP 2001.
12. methods as described in any one in claim 1-6, wherein, described solvent is: water, Virahol or its combination.
13. methods as claimed in claim 3, wherein, described esters of unsaturated carboxylic acids is: the combination of one or more in butyl acrylate, butyl methacrylate, isobutyl acrylate, the misery butyl ester of propylene and Octyl methacrylate.
14. methods as claimed in claim 4, wherein, described pH buffer reagent is: the combination of one or more in carbonate, phosphoric acid salt and pyrophosphate salt.
15. methods as claimed in claim 5, wherein, described chain-transfer agent is: tert-dodecyl mercaptan, dodecyl mercaptan carbon or its combination.
16. methods as claimed in claim 6, wherein, described structural reinforcing agent is: triazines nitrogen-containing heterocycle compound, trifunctional base aziridine cpd or its combination.
17. the method for claim 1, it does not comprise sulfur cross-linking agent.
18. the method for claim 1, wherein, the preparation of described mixture is to be first a premixture by described vinyl cyanide, described functional monomer, described emulsifying agent and described solvent, then add described divinyl and described initiator in described premixture to form described mixture.
19. the method for claim 1, wherein step b carry out 7.0 to 15.0 hours.
20. the method for claim 1, wherein step c carry out 2.0 to 6.0 hours.
21. the method for claim 1, wherein steps d carry out 4.5 to 8.5 hours.
22. methods as claimed in claim 19, wherein, after step b completes, within 30 minutes by temperature increase to 35 to 45 ℃, to carry out described step c.
23. methods as claimed in claim 20, wherein, after step c completes, within 30 minutes by temperature increase to 45 to 55 ℃, to carry out described steps d.
24. methods as claimed in claim 19, wherein, after step b completes, add after an emulsifying agent and a reductive agent, then carry out described step c.
25. methods as claimed in claim 20, wherein, after step c completes, add after an emulsifying agent and a reductive agent, then carry out described steps d.
26. methods as described in claim 24 or 25, wherein, described emulsifying agent is one or more the combination in sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, oxyethane lauryl alcohol and Voranol EP 2001.
27. methods as described in claim 24 or 25, wherein, described reductive agent is one or more the combination in Sodium Metabisulphate 65, sodium bisulfite and ferrous sulfate.
28. the method for claim 1, wherein the addition of the described terminator of step e be 50 to 400ppm.
29. methods as claimed in claim 28, wherein, described terminator is one or more the combination in Sodium dimethyldithiocarbamate 40min, Thiocarb, potassium dimethyldithiocarbamate sodium, dimethyl dithiocarbamic acid ammonium, Resorcinol and diethyl hydroxylamine.
30. the method for claim 1, wherein step e further comprise that to adjust pH value be 7.5 to 8.5.
31. the method for claim 1, wherein step e further comprise add a deodorization agent.
32. methods as claimed in claim 31, wherein, described deodorization agent is Acrylic emulsion deodovization agent.
33. the method for claim 1, wherein step e further comprise add a defoamer.
34. methods as claimed in claim 33, wherein, described defoamer is organosilicon polymer, Dormant oils or its combination.
35. the method for claim 1, it further comprises a step f after step e, and described step f is in-3.0 to-5.0Kgf/cm
2pressure under carry out following steps:
Import nitrogen;
Bleed, and stir through the reacted mixture of step e;
Stop importing nitrogen;
Stop bleeding; And
Carry out filtration step.
36. the method for claim 1, it is to carry out at the temperature of in 10 to 55 ℃.
37. the method for claim 1, its transformation efficiency is minimum is 90%.
38. methods as claimed in claim 37, its transformation efficiency is minimum is 96%.
39. 1 kinds of carboxyl butyronitrile latex products, it is to make take the prepared carboxyl butyronitrile latex of the method described in any one in claim 1-38 as raw material, its tensile strength is 20 to 25Mpa, and its unit elongation is 550 to 700%.
40. carboxyl butyronitrile latex products as claimed in claim 39, it is gloves or dress ornament.
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| TW101140069A TWI481629B (en) | 2012-10-30 | 2012-10-30 | Method for nitrile butadiene rubber latex production and articles made by using the nitrile butadiene rubber latex |
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| JP (1) | JP5719388B2 (en) |
| CN (1) | CN103788298A (en) |
| TW (1) | TWI481629B (en) |
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| WO2019181697A1 (en) * | 2018-03-22 | 2019-09-26 | 日本ゼオン株式会社 | METHOD FOR RECOVERING UNREACTED α,β-ETHYLENICALLY UNSATURATED NITRILE MONOMER CONTAINED IN LATEX OF CARBOXYL GROUP-CONTAINING NITRILE RUBBER |
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| CN113286846A (en) * | 2019-10-01 | 2021-08-20 | 株式会社Lg化学 | Latex composition for dip molding, dip molded product comprising the same, and method for manufacturing dip molded product using the same |
| CN113480691A (en) * | 2021-08-25 | 2021-10-08 | 河北中宫睿宸医用新材料科技有限公司 | Carboxyl butyronitrile latex for gloves and preparation method thereof |
| CN113773565A (en) * | 2021-09-15 | 2021-12-10 | 中国热带农业科学院农产品加工研究所 | Sulfur-free vulcanized carboxylic nitrile latex and vulcanization method and application thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP5719388B2 (en) | 2015-05-20 |
| TWI481629B (en) | 2015-04-21 |
| JP2014088536A (en) | 2014-05-15 |
| TW201416381A (en) | 2014-05-01 |
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